Synthesis of anatase tio2



United States Patent .'.13,488,149- SYNTHESIS OF ANATASE Ti0 Joseph FrancisSkrivan, Stamford, Conn., assignor to American Cyanarnid Company, Stamford, Conn., a corv poration of Maine 1 I No Drawing. Filed Dec. 1, 1965, Ser. No. 510,938

Int. Cl. C01g 23/04 U.S. Cl. 23-202 4 Claims This invention relatesbroadly to a process for the preparation of a specific crystalline form of finely divided titanium dioxideaMore particularly, it relates to the preparation of..a new anatase titanium dioxide composition byhigh temperature hydrolysis or oxidation of titanium tetrachlorde. Moreover, it relates to the new compositions thus prepared.

Titanium dioxide is known to exist in several crystalline forms including the rutile and anatase forms. Each form has its own characteristics and special qualities making it more desirable than the other for certain end uses. For example, the anatase form,'because of its bluish-white tint tone and chalking characteristics, is sometimes preferred for outdoor white paints where a self-cleaning protective coating is needed. There are many applications which require use of the more stable non-chalking rutile form.

Various methods'of producing titanium dioxide in its various crystalline forms are known 'at the present time. One method used to produce anatase TiO- involves the digestion of titaniferous ore material with sulfuric acid to produce titanium'"'sulphate.' T he sulphate is hydrolyzed to precipitatehydrous TiOjJThis may be calcined to give particulat'eTiO of theianatase form. It is often necessary to subject the "product'to further treatment if it is desired to improve its quality" for'pigmentapplication.

Another known method of producing titanium dioxide is to react titanium tetrachloride with oxygen at an elevated temperature. In this method, the reactants are broughtto Another method for producing TiO is a hydrolysis mechanism characterized by the step of contactingvapor-- ous TiCl, with the combustion product of any hydrogencontaining material. Like other known vapor phase-processes, this leads to a product which is a mixture of the anatase and rutile forms, there being no known means to I,

substantially increase the amount offa natasei Still another known method forpr'epafirfg TiOyinvolves the oxidation of TiCl, in a plasmai-stream'g'ln this method a very excellent product is obtained insofar a's'a" particle content.

In general, it has been the case until the present time that TiO of very high rutile content could be obtained from efficient vapor phase procedures with use of proper promoters whereas TiO products with very high anatase content (i.e., above 60%), were not directly obtainable by high temperature, vapor phase processes and could only be obtained by the inefficient sulfuric acid digestion process.

In view of the state of the art, it is an object of this invention to provide a means of preparing titanium dioxide in substantially pure anatase form by the vapor phase conversion of a volatile salt of titanium.

It is another object of this invention to provide a new titanium dioxide composition having a high anatase content and a minor amount of boron oxide.

Other objects of the invention will be evident from the following detailed description thereof.

In accordance with this invention, it has been found that these objects can be accomplished in a surprisingly simple and effective manner. The method of this invention merely involves oxidizing or hydrolyzing the vaporous titanium starting material in the presence of a small amount of a volatilized boron compound, or the metal itself. When the hydrolysis or oxidation is thus conducted, the product is obtained essentially in the anatase form of TiO The method of this invention provides the first known means of obtaining anatase TiO from a high temperature process. It is most surprising that it works at all, since the presence of other metals (or compounds thereof) of the same periodic classification as boron (i.e., Group III), is known to have the opposite effect. Thus, use of aluminum chloride instead of boron chloride promotes the formation of the rutile form of TiO The present invention thus provides an unobvious way of increasing the anatase content of a TiO product over what is heretofore obtainable. It should be noted that in general a vapor phase conversion of titanium-containing material to TiO normally leads to a product having substantial amounts (at least about 40-50%) of the rutile crystalline form. By following the present invention, it is possible to increase the amount of the anatase form by any increment, depending upon the amount of the boron material added to the oxidation mixture; and also depending upon the presence of other materials which may perform a useful function while to some extent nullifying theelfect of the boron material: For example,--if-the-conversion to TiO is conducted in the presence of a boron material and a nucleating agent (e.g., AlCl interesting and useful effects can be obtained. The. boron material hasas its effect; the promotionof-anatase formation. The

AlCl, effects a reduction of particle size, but also counteracts the effect of the boron material. Therefore, theprodnot made in the presence of the boron and aluminum materials will have a larger proportion of small particles (which is. desirable forcmanypigment purposes) anda lower anatase content (which can be tolerated in'many applications). Such a product would be highly useful in the preparation of chalking outdoor white paints where 10-15% of the rutile form of TiO is tolerable.

' In other situations, it is very critical to have almost no rutile form in the Tio 'material. For example, in paper manufacture, a-large user of anatase TiO the presence a of rutile TiO is extremely undesirable in view of the size distribution is concerned aridby use-"of arntire'p're mixture of anatase and rutile forms of TiO, which is not abrasiveness of this material and its dulling effect on paper-cutting knives. Tolerances of the rutile form of TiO in this case are generally less than 23% and the rial to the vaporous titanium starting material since some" other materials might tend to give an adversely high rutile content in the product.

The present invention thus is not limited to the production of substantially pure anatase TiO but rather resides in a new means for increasing anatase content as may be desired for the specific intended end use of the TiO- product.

For the purpose of the present invention, any form of boron, either elemental or chemically combined, may be added to the titanium starting material. Solid forms of boron can be conveniently used by either vaporizing or com minuting the same before addition to the titanium reactant stream. Among the useful boron compounds are boron trichloride, boron trifiuoride (for hydrolysis reactions), boron sulfide, boron hydrides and boron oxide. The amount of boron compound which is to be used depends upon the desired anatase content of product TiO In general, it is desirable to use as little as necessary, and for most purposes, 0.1-10% B based on the weight of the titanium dioxide is sutlicient. Within this range, it will be found that l6% of the boron material gives the desired effect with minimal loss of T10 tinting strength.

The process of this invention can be adjusted to the framework of any vapor phase conversion of a titanium salt. It can be used with plasma jet processes, flame processes (either laminar or turbulent) or hydrolysis processes in which volatile salts of titanium such as the halides or oxyhalides are feed reactants. In all cases, the principal of operation is the same with respect to the present invention, i.e., a boron compound, or boron itself in a vaporous form, is present in the zone in which TiO is being formed. To permit this, the boron material is added to either the titanium starting material, the oxidizing or hydrolyzing reactant, or even to a pre-formed mixture of the two, providing it has not reached reaction temperature at the time of the addition.

Example 7 Into a burner of the type shown in US. Patent 3,121,641, issued Feb. 18, 1964, having both burner tubes 6" in diameter, is fed a gas mixture containing 23.9 liters/minute of TiCl "1.1 liters/minute of -BCl vapor, 65 liters/minute of CO,"arid ZOO'Iitei's/minute of 0 (all measured at 0., and l'atrnos'pherepres's'ufe but preheated to 250 C.)." Thi s ga's" mixture' i s dividedjequally between the two tubes..fIhe solid pxide'p'roductis found to contain 93% anatase.

Example 8 adjusted so that a stableflameispbtained. The solid TiO The following examples are presented to further illustrate the present invention.

Examples 1-6 TiCl Nitrogen plasma (3.2 lbs/hour each stream) hav- 7 ing a temperature of at least 3000 C. was used to supply heat to the O and TiCl, streams. Results of these experiments are given in the table which follows.

collected from this operation contains 97% anatase.

f eam: 9

The procedure of Example 8 is followed 'usingboron oxide instead of boront'richloride"as the anatase promoter.

' The oxide product is found to contain substantially the same amount of anatase.

Example 10 When the procedure of Example 8 is followed using boron sulfide, it is found that the oxide product is substantially the same with respect tothe .anatase content.

Iclaim: I

1. The process of-pre'paring finely divided titanium dioxide having at least by weight anatase crystalline form which comprises converting a volatile titanium salt to said dioxide in the presence of about 0.1 to 10% by weight of a boron material based on titanium dioxide, said conversion being effected in the vapor phase.

2. The process of claim 1 wherein said boron material isboron tn'chloride. 1 v

3. The process of claim 2 wherein said boron trichloride is admixed withsilicon tetrachloride.

4. The process of claim 1 wherein said titanium salt is converted by. a vapor phase oxidation reaction using a plasma stream of at least 3000", C. temperature as the preheat source.

TABLE Number Wt. Percent Avg. Wt. Per- (based on TiCh Flow 01 Flow Particle cent Oxide Rate Rate Diam. Anatase Example Additive Product) (lbs./hr.) (lbs./hr.) (u) inProduct 1 Average particle diameter as determined on a number basis.

References Cited ,YUNITED 1STATES" PATENTS"' 

